Fluorecent reactive dyes, process for the production thereof and their use

ABSTRACT

The present invention is directed to fluorescent reactive dyes of general formula (I) 
     
       
         
         
             
             
         
       
     
     a process for the production thereof and their use.

The present invention relates to the technical field of reactivedyestuffs for dyeing and printing of hydroxyl-, amino- and/orcarboxamido-containing material.

Fluorescent reactive dyes are known from prior art and can be used ascolorants in different applications, see for example DE 2337488, EP153480, DE 2442839 and DE 1955849.

However, in the context of the dyeing and printing of hydroxyl-, amino-and/or carboxamido-containing material the known dyes with fluorescenceproperties have a number of technical disadvantages such asunsatisfactory light fastness and especially limitations in built up andother dyeing properties especially in exhaust processes.

Surprisingly, it has now been found that the dyes of formula (I) asdescribed below show highly advantageous properties over the known dyes.These dyes with two or more reactive anchors show good fluorescentproperties also in combination/in mixtures with other fluorescent dyesand good overall fastness properties on the materials mentioned aboveand on blends containing them.

Some dye(s) of general formula (I)

-   -   wherein in each case independent from each other    -   W is O, S or NH,    -   R¹ and R² is hydrogen, alkyl, alkyl substituted by one or more        substituents selected from the group consisting of methoxy,        hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by        one or more substituents selected from the group consisting of        chloro, acetylamino, sulfo, hydroxy, carboxy, (C₁-C₄)-alkanoyl,        (C₁-C₄)-alkoxy and (C₁-C₄)-alkyl or benzyl,    -   R³ and R⁴ is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy,        thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO₃M,        COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl,        trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl,        alkoxythiocarbonyl, acyloxy, aryloyloxy or SO₂—X,        -   wherein X is vinyl or CH₂CH₂—Y,            -   wherein Y is a group removable under alkaline                conditions,    -   Z⁻ is an anion,    -   A¹ and A² is a spacer and    -   T¹ and T² is a reactive anchor    -   have such advantageous technical properties.

The chromophore in this invention is a group having the followingstructure:

Attached to it are the spacers A¹ and A².

A group removable under alkaline conditions, is a group which will leavethe molecule under alkaline conditions to yield a vinyl sulfone.Non-limiting examples of such groups are OSO₃M, SSO₃M, OCOCH₃, OPO₃M andhalogen.

The anion is defined by the production and/or purification process.Non-limiting examples of anions are halogen, sulfates, benzolsulfonates,toluolsulfonates, tetraborofluorates or acetates. Preferred arechloride, bromide and sulfates.

A spacer is a group that can react on one side with thechromophore/chromophore precursor and with a second reaction center ofthe molecule with a reactive anchor. A spacer can be aliphatic-,aromatic- or mixed aliphatic/aromatic. Non-limiting examples aresubstituted- or unsubstituted-alkylen-diamines for aliphatic-spacers,substituted- or unsubstituted-aniline-/naphthaline-diamines foraromatic-spacers and aminoalkyl substituted anilines-/naphthalines- formixed aliphatic/aromatic-spacers.

A reactive anchor is a group that is directly fixed with a covalent bondto the chromophor or via a spacer that can form a covalent bond tohydroxyl-, amino- and/or carboxamido-containing fibre. This can beachieved with groups having activated leaving groups, such as halogen orOSO₃H, which can be replaced in a nucleophilic substitution reaction bythe hydroxyl-, amino- and/or carboxamido-containing fibre. Non-limitingexamples are: β-chloroethylsulfonyl-groups, 2,3-dibromo-propionic acidderivatives (CO—CHBr—CH₂Br) and β-sulfatoethylsulfonyl groups and2,3-dichloro-quinoxaline.

A second reaction type to form a covalent bond to hydroxyl-, amino-and/or carboxamido-containing material is the nucleophilic addition toan activated carbon-carbon double bond by the hydroxyl-, amino-groups ofthe fibre.

Non-limiting examples are: bromo-acrylic (CO—CBr═CH₂)-acid derivativesand vinylsulfones (SO₂—CH═CH₂).

The invention is directed to a dye of formula (I)

wherein in each case independent from each other

-   -   W is O, S or NH,    -   R¹ and R² is hydrogen, alkyl, alkyl substituted by one or more        substituents selected from the group consisting of methoxy,        hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by        one or more substituents selected from the group consisting of        chloro, acetylamino, sulfo, hydroxy, carboxy, (C₁-C₄)-alkanoyl,        (C₁-C₄-alkoxy and (C₁-C₄-alkyl or benzyl,    -   R³ and R⁴ is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy,        thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO₃M,        COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl,        trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl,        alkoxythiocarbonyl, acyloxy, aryloyloxy or SO₂—X,        -   wherein X is vinyl or CH₂CH₂—Y,            -   wherein Y is a group removable under alkaline                conditions,    -   Z⁻ is selected from the group consisting of halogen, sulfate,        alkylsulfonate, benzolsulfonate, toluolsulfonate,        tetraborofluorate and acetate,    -   A¹ and A² is a spacer of formula (2c) or (2d)

-   -   -   whereby the respective spacer A¹/A² is attached to the            chromophore at the * position and to the respective reactive            anchor T¹/T² at the ** position, and wherein            -   d is an integer from 1 to 4,            -   e is an integer from 0 to 3,            -   f is an integer from 0 to 3,            -   g is an integer from 0 to 3,            -   Q is O, NH or S,            -   R⁶ is hydrogen, halogen, alkyl, N-acylamino, alkoxy,                thioalkoxy, hydroxy, alkoxycarbonyl, acyl, arylol,                acyloxy, aryloyloxy, cycloalkyl, aryl, SO₃M or COOM,            -   R⁸ and R⁹ is hydrogen, alkyl, alkoxy, aryl, hydroxyl,                NH—CH₂—CH₂—OSO₃H, SO₃M or COOM,

    -   T¹ and T² is a reactive anchor of formula (3d), (3e) or SO₂—X

-   -   -   whereby the respective reactive anchor T¹/T² is attached to            the respective spacer A¹/A² at the *** position, and wherein            -   X is vinyl or CH₂CH₂—Y,                -   wherein Y is a group removable under alkaline                    conditions,

    -   and

    -   M is hydrogen, lithium, sodium, potassium, ammonium, mono-, di-,        tri- or tetra-(C₁-C₄)-alkylammonium, one equivalent of an alkali        earth metal or a monovalent organic cation.

This invention refers to all kinds of tautomeric and geometric isomersof the dyes of the formula (I).

Alkyl groups in this invention may be straight-chain or branched and are(C₁-C₁₂)-alkyl groups, preferably (C₁-C₈)-alkyl groups, for examplen-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl,sec-butyl, tert-butyl and methylbutyl.

The same applies for alkoxy groups, which accordingly are preferably(C₁-C₈)-alkoxy, for example methoxy and ethoxy, to thioalkoxy groups,which are preferably (C₁-C₈)-thioalkoxy, for example —SCH₃ and —SC₂H₅.

Cycloalkyl groups are preferably (C₃-C₈)-cycloalkyl. Particularlypreferred are cyclopentyl and cyclohexyl. The term cyloalkyl comprisesfor the purpose of the present invention substituted cycloalklyl groupsand unsaturated cycloalkyl groups as well. A preferred group of thistype is cyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl,halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino,dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino,monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Aryl groups appearing in this invention are preferably phenyl ornaphthyl. The terms phenyl and naphthyl comprise unsubstituted as wellas substituted phenyl and naphthyl. Preferred substituents are alkyl,cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy,alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino,mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino,monoalkyl-mono-(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heteroaryl groups appearing in this invention are preferably pyridine,pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole,1,2,4-thiadiazole, 1,2,4-triazole, tetrazole, thiophene, thiazole,isothiazole, benzothiazole, benzoisothiazole, 1,3,4-thiadiazole, furane,oxazole, benzoxazole or isoxazole. The term heteroaryl comprises theabove groups in unsubstituted as well as in substituted form. Preferredsubstituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy,alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino,mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino,monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heterocycloalkyl groups are preferably pyrrolidine, piperidine,morpholine, tetrahydrofuran or piperazine. The term heterocycloalkylcomprises the above groups in unsubstituted as well as in substitutedform. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl,alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino,dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxylalkyl)amino,monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,aminocarbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Halogen is preferably chlorine, bromine or fluorine.

M is preferably hydrogen, lithium, sodium or potassium.

There exist preferred embodiments of the invention. The first preferredembodiment is characterized by the fact that both reactive anchors T¹and T² are vinylsulfone- (SO₂—CH═CH₂) and/or β-sulfatoethylsulfonyl-groups (SO₂—CH₂—CH₂—OSO₃H).

More preferred is a dye as described above, wherein in each caseindependent from each other

-   -   W is O or S,    -   R¹ and R² is hydrogen, alkyl, alkyl substituted by one or more        substituents selected from the group consisting of methoxy,        hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by        one or more substituents selected from the group consisting of        chloro, acetylamino, sulfo, hydroxy, carboxy, (C₁-C₂)-alkanoyl,        (C₁-C₂)-alkoxy and (C₁-C₂)-alkyl or benzyl,    -   R³ and R⁴ is hydrogen, (C₁-C₄)-alkyl, hydroxy, aryl,        (C₁-C₄)-alkoxy, N-acylamino, halogen, SO₃M, COOM, acyl,        (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonyl or SO₂—X,        -   wherein X is vinyl or CH₂CH₂—Y,            -   wherein Y is a group removable under alkaline                conditions,    -   Z⁻ is selected from the group consisting of halogen, sulfate,        alkylsulfonate, benzolsulfonate, toluolsulfonate,        tetraborofluorate and acetate,    -   A¹ and A² is a spacer of formula (2c) or (2d)

-   -   whereby the respective spacer A¹/A² is attached to the        chromophore at the * position and to the respective reactive        anchor T¹/T² at the ** position, and wherein        -   d is 1 or 2,        -   e is 0 or 1,        -   f is 0        -   g is 0 or 1,        -   Q is O or S,        -   R⁶ is hydrogen, (C₁-C₄)-alkyl, N-acylamino, (C₁-C₄)-alkoxy,            acyl, benzyl, SO₃M or COOM        -   R⁸ and R⁹ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, SO₃M            or COOM,    -   T¹ and 1² is SO₂—X,        -   wherein X is vinyl or CH₂CH₂—Y,            -   wherein Y is a group removable under alkaline conditions    -   and    -   M is hydrogen, lithium, sodium, potassium, one equivalent of an        alkali earth metal or a monovalent organic cation.

And most preferred is a dye as described above, wherein in each caseindependent from each other

-   -   W is oxygen,    -   R¹ and R² is hydrogen, (C₁-C₄-alkyl, aryl or benzyl,    -   R³ and R⁴ is hydrogen, (C₁-C₂)-alkyl, halogen, SO₃M, COOM or        SO₂—X,        -   wherein X is vinyl or CH₂CH₂—Y,            -   wherein Y is a group removable under alkaline                conditions,    -   Z⁻ is selected from the group consisting of halogen, sulfate,        alkylsulfonate, benzolsulfonate, toluolsulfonate,        tetraborofluorate and acetate,    -   A¹ and A² is a spacer of formula (2c-1) or (2d-1)

-   -   whereby the respective spacer A¹/A² is attached to the        chromophore at the * position and to the respective reactive        anchor T¹/T² at the ** position, and wherein        -   d is 1 or 2,        -   e is 0 or 1,        -   g is 0 or 1,        -   Q is oxygen,        -   R⁶ is hydrogen or (C₁-C₂)-alkyl,        -   R⁸ and R⁹ is hydrogen, (C₁-C₂)-alkyl, (C₁-C₂)-alkoxy or            SO₃M,    -   T¹ and T² is SO₂—X,        -   wherein X is vinyl or CH₂CH₂—Y,            -   wherein Y is a group removable under alkaline conditions    -   and    -   M is hydrogen, lithium, sodium, potassium, one equivalent of an        alkali earth metal or a monovalent organic cation.

The dyes of the present invention can be produced in different ways.Thus the invention is also directed to two processes for the productionof the inventive dyes.

A process for the production of dyes as described above comprising thesteps of:

-   -   a) Reacting one 3,6,9 substituted 9H-Xanthene, wherein the 3-        and 6-substituents react as a leaving group, with two        precursor-amines H—NR¹-A¹-T¹ and H—NR²-A²-T² of identical or        different spacer-reactive-anchor-units on 3- and 6-position,    -   b) Sulfonating the OH-groups with concentrated sulfuric acid        thus forms an aspect of the present invention.

And a process for the production of dyes as described above comprisingthe steps of:

-   -   reacting    -   one 3,6,9 substituted 9H-Xanthene, wherein the 3- and        6-substituents react as a leaving group, with        -   a) two identical aliphatic-, aromatic- or mixed            aliphatic/aromatic-amines symmetrically on both 3- and            6-position,        -   or        -   b) one aliphatic-, aromatic- or mixed            aliphatic/aromatic-amine for the 3-position in a first step            -   and            -   one aliphatic-, aromatic- or mixed                aliphatic/aromatic-amine, which is different to the                first one, for the 6-position in a second step        -   or        -   c) one aliphatic-, aromatic- or mixed            aliphatic/aromatic-amine for the 6-position in a first step            -   and            -   one aliphatic-, aromatic- or mixed                aliphatic/aromatic-amine, which is different to the                first one, for the 3-position in a second step    -   and further reacting the products resulting from a), b) or c)        respectively with reactive anchor groups        forms another aspect of the present invention.

The compounds, which lead to the sections of the dye-molecule havingformula (2c), (2c-1), (2d), (2d-1), (3d) and (3e) are known andcommercially available or can be synthesised by means of common chemicalreactions known to a person skilled in the art (see e.g. UllmannsEncyclopedia of Industrial Chemistry; Houben-Weil, Methods of OrganicChemistry).

The end product, which contains β-sulfatoethylsulfonyl-groups canoptionally also be subjected to a vinylization reaction. For example, avinylizable reaction group such as β-sulfatoethylsulfonyl is convertedinto its vinyl form. Such reactions are known to a person skilled in theart. They are generally performed in a neutral to alkaline medium at atemperature, for example, from 20 to 80° C., at a pH of, for example,from 7 to 10.

The dyes of formula (I) are fiber-reactive, i.e. are containingfiber-reactive functional rests. Fiber-reactive functional rests referto rests capable of reacting with the hydroxyl groups of cellulosicmaterials, the amino, carboxyl, hydroxyl and thiol groups in the case ofwool and silk, or with the amino and possibly carboxyl groups ofsynthetic polyamides to form covalent chemical bonds.

The dyes of the present invention are suitable for dyeing and printingof natural, manufactured, regenerated, mechanically or chemicallymodified, recycled or synthetic hydroxyl-, amino-, and/orcarboxamido-containing fiber materials and their blends by theapplication methods numerously described in the art for reactive dyes.

Thus a process for dyeing or printing carboxamido- and/orhydroxyl-containing material, comprising contacting the carboxamido-and/or hydroxyl-containing material with a dye as described above formsanother aspect of the present invention.

Examples of natural fibre materials as described above are vegetablefibres such as seed fibres i.e. cotton, organic cotton, kapok, coir fromcoconut husk; bast fibers i.e. flax, hemp, jute, kenaf, ramie, rattan;leaf fibres i.e. sisal, henequen, banana; stalk fibres i.e. bamboo; andfibres from animals such as wool, organic wool, silk, cashmere wool,alpaca fiber, mohair, Angora fibre as well as fur and leather materials.

Examples of manufactured and regenerated fibres are cellulosic fibressuch as paper and cellulosic regenerated fibres such as viscose rayonfibres, acetate and triacetate fibers and Lyocell fibers.

Examples of synthetic fiber materials as described above are nylonmaterials, like nylon-6, nylon-6.6 and aramid fibres.

The above-mentioned substrates to be dyed can be present in variousforms such as but not limited to yarn, woven fabric, loop-forminglyknitted fabric or carpet.

Fiber and blends containing such fiber selected from the groupconsisting of: synthetic fiber materials, nylon materials, nylon-6,nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton,organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp,jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalkfibres, bamboo; fibres from animals, wool, organic wool, silk, cashmerewool, alpaca fiber, mohair, Angora fibre as well as fur and leathermaterials; manufactured, regenerated and recycled fibres, cellulosicfibres; paper fibres, cellulosic regenerated fibres, viscose rayonfibres, acetate and triacetate fibers, and Lyocell fibers comprising oneor more dye(s) as described above either in chemically and/or physicallybound form thus forms another aspect of the present invention.

The dyes of the present invention and their salts or mixtures can beused as a single dyeing product in dyeing or printing processes or itcan be part of a di/tri or multi-component combination product in dyeingor in printing compositions.

The use of a dye as described above, a chemical composition or of anaqueous solution as described below for dying fibers, as well as blendsof such fibres selected from the group consisting of; synthetic fibermaterials, nylon materials, nylon-6, nylon-6.6 and aramid fibres,vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir fromcoconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaffibres, sisal, henequen, banana; stalk fibres, bamboo; fibres fromanimals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair,Angora fibre as well as fur and leather materials; manufactured,regenerated and recycled fibres, cellulosic fibres; paper fibres,cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibers and Lyocell fibers is another aspect of the presentinvention.

Dyes of this invention and their salts or mixtures are highly compatiblewith other known and/or commercially available dyes and they can be usedtogether with such dyes to obtain specific hues of similarly goodtechnical performance, Technical performance includes build-up, fastnessproperties and levelness.

A chemical composition comprising one or more dye(s) of the presentinvention forms yet another aspect of the present invention.

Since the water solubility of the dyes according to the invention isvery good, they can also be used with advantage in customary continuousdyeing processes.

The dyes of the present invention can also be used in digital printingprocesses, in particular in digital textile printing. An aqueoussolution for dying comprising one or more chemical compounds asdescribed above forms still another aspect of the present invention.

As does an ink for digital textile printing, comprising a dye of thepresent invention.

The inks of the present invention comprise the dye of the presentinvention in amounts which preferably range from 0.1% by weight to 50%by weight, more preferably from 1% by weight to 30% by weight and mostpreferably from 1% by weight to 15% by weight, based on the total weightof the ink.

The inks, as well as the dyes of the present invention may, if desired,contain further dyes used in digital printing.

For the inks of the present invention to be used in the continuous flowprocess, a conductivity of 0.5 to 25 mS/m can be set by adding anelectrolyte. Useful electrolytes include for example lithium nitrate andpotassium nitrate. The inks of the present invention may include organicsolvents at a total level of 1-50% and preferably 5-30% by weight.Suitable organic solvents are for example alcohols, for examplemethanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butanol,pentyl alcohol, polyhydric alcohols for example: 1,2-ethanediol,1,2,3-propanetriol, butanediol, 1,3-butanediol, 1,4-butanediol,1,2-propanediol, 2,3-propanediol, pentanediol, 1,4-pentanediol,1,5-pentanediol, hexanediol, D,L-1,2-hexanediol, 1,6-hexanediol,1,2,6-hexanetriol, 1,2-octanediol, polyalkylene glycols, for example:polyethylene glycol, polypropylene glycol, alkylene glycols having 1 to8 alkylene groups, for example: monoethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol,butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol,tripropylene glycol, low alkyl ethers of polyhydric alcohols, forexample: ethylene glycol monomethyl ether, ethylene glycol monoethylether, ethylene glycol monobutyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, diethylene glycol monobutylether, diethylene glycol monohexyl ether, triethylene glycol monomethylether, triethylene glycol monobutyl ether, tripropylene glycolmonomethyl ether, tetraethylene glycol monomethyl ether, tetraethyleneglycol monobutyl ether, tetraethylene glycol dimethyl ether, propyleneglycol monomethyl ether, propylene glycol monoethyl ether, propyleneglycol monobutyl ether, tripropylene glycol isopropyl ether,polyalkylene glycol ethers, such as for example: polyethylene glycolmonomethyl ether, polypropylene glycol glycerol ether, polyethyleneglycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines,such as for example: methylamine, ethylamine, triethylamine,diethylamine, dimethylamine, trimethylamine, dibutylamine,diethanolamine, triethanolamine, N-acetylethanolamine,N-formylethanolamine, ethylenediamine, urea derivatives, such as forexample: urea, thiourea, N-methylurea, N,N′-epsilon dimethylurea,ethyleneurea, 1,1,3,3-tetramethylurea, amides, such as for example:dimethylformamide, dimethylacetamide, acetamide, ketones or ketoalcohols, such as for example: acetone, diacetone alcohol, cyclicethers, such as for example: tetrahydrofuran, trimethylolethane,trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol,gamma butyrolactone, epsilon-caprolactam, further sulfolane,dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethylsulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide,N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, M-ethylpyrrolidone,2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone,1-(3-hydroxypropyl)-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,1,3-dimethyl-2-imidazolinone, 1,3-bismethoxymethylimidazolidine,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, pyridine,piperidine, butyrolactone, trimethylpropane, 1,2-dimethoxypropane,dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether,1,2-dimethoxypropane and trimethylpropane.

The inks of the invention may further include customary additives, forexample viscosity moderators to set viscosities in the range from 1.5 to40.0 mPas in a temperature range from 20 to 50° C. Preferred inks have aviscosity of 1.5 to 20 mPas and particularly preferred inks have aviscosity of 1.5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example:polyvinylcaprolactam, polyvinylpyrrolidone and their copolymerspolyetherpolyol, associative thickeners, polyurea, polyurethane, sodiumalginates, modified galactomannans, polyetherurea, polyurethane,nonionic cellulose ethers.

As further additives the inks of the invention may includesurface-active substances to set surface tensions of 20 to 65 mN/m,which are adapted if necessary as a function of the process used(thermal or piezo technology). Useful surface-active substances includefor example all surfactants, preferably nonionic surfactants,butyldiglycol and 1,2-hexanediol.

The inks of the present invention may further include customaryadditives, for example substances to inhibit fungal and bacterial growthin amounts from 0.01 to 1% by weight based on the total weight of theink.

The inks may be prepared in a conventional manner by mixing thecomponents in water.

The inks of the present invention are particularly useful in inkjetprinting processes for printing a wide variety of materials, inparticular of wool and polyamide fibers.

The examples below serve to illustrate the invention. Parts andpercentages are by weight unless noted otherwise. The relationshipbetween parts by weight and parts by volume is that of the kilogram tothe liter.

EXAMPLE 1

50 parts of 2-sulfobenzoic acid anhydride were added to 246 parts ofPOCl₃ under stirring. After 30 minutes 58 parts of resorcinol(3-hydroxy-phenol) were added and the mixture was heated to 95° C. andstirred for 2 hours. The reaction mixture was cooled down to 5° C. andadded to 3000 parts of a 5° C. cold 20% ic aqueous NaCl solution. Thesuspension was stirred for 30 minutes at 0 to 5° C. and filtrated. Theisolated wet press paste was suspended in 200 parts of acetone andstirred for 20 minutes at 5° C. After filtration and drying 27 parts ofdichloro-sulfophenyl-xanthen were isolated.

1. Condensation: 10.13 parts of dichloro-sulfophenyl-xanthen were mixedtogether with 5.73 parts of n-ethyl-3 (β-hydroxyethy)sulfonylanilin/(2-(3-ethylamino-benzenesulfonyl)-ethanol) as amine 1 in 100 mlof water and the pH was adjusted to 5.0. The reaction mixture was heatedto 60° C. and stirred and the pH was kept at 5.0 with a 15% ic Na₂CO₃solution.

2. Condensation: After 1 hour 4.9 parts of2-(2-methylamino-ethanesulfonyl)-ethanol as amine 2 were added and thepH was adjusted to 9.0 and the reaction mixture was heated to 90° C. andstirred for 3 hours.

The reaction mix was cooled to room temperature and the water wasevaporated under reduced pressure delivering 20.5 parts of Intermediate1 after drying under vacuum conditions.

Sulfonation: 17.52 parts of Intermediate 1 were added in portions to 110parts sulfuric acid (98 to 100%) at 20 to 60° C. The reaction mixturewas stirred for 3 h at 60° C. and then cooled to 0 to 5° C. This mixturewas added to 300 parts of ice at 0° C., the pH was adjusted with CaCO₃to 5.3. The CaSO₄ was filtered and the product in the filtrated solutionwas isolated by vacuum rotary evaporation and dried under vacuumconditions resulting in 16 parts of example 1 that dyes cotton inbrilliant fluorescent red shades.

Example 1 EXAMPLE 2

1. Condensation: 10.13 parts of Dichloro-sulfophenyl-xanthen were mixedtogether with 5.73 parts of n-ethyl-3 (β-hydroxyethy)sulfonyl anilin2-(3-ethylamino-benzenesulfonyl)-ethanol as amine 1 in 100 ml of waterand the pH was adjusted to 5.0. The reaction mixture was heated to 60°C. and stirred and the pH was kept at 5.0 with a 15% ic Na₂CO₃ solution.

2. Condensation: After 1 hour 4.9 parts2-(2-chloro-ethanesulfonyl)-ethylamine as amine 2 were added and the pHwas adjusted to 9.0 and the reaction mixture was heated to 90° C. andstirred for 3 hours.

The reaction mix was cooled to room temperature and the water wasevaporated under reduced pressure delivering 20.5 parts of Intermediate1 after drying under vacuum conditions.

Sulfonation: 17.52 parts of Intermediate 1 were added in portions to 110parts sulfuric acid (98 to 100%) at 20 to 60° C. The reaction mixturewas stirred for 3 h at 60° C. and then cooled to 0 to 5° C. This mixturewas added to 300 parts of ice at 0° C., the pH was adjusted with CaCO₃to 5.3. The CaSO₄ was filtered and the product in the filtrated solutionwas isolated by vacuum rotary evaporation and dried under vacuumconditions resulting in 16 parts of example 1 that dyes cotton inbrilliant fluorescent red shades.

Example 2 EXAMPLE 3 TO 39

According to example 1 or 2 the following amines can be used for 1.Condensation (Amine 1) and for 2. Condensation (Amine 2). Aftersulfonation and isolation according to example 1 or 2 dyes having thegiven colours are obtained when using amines 1 and 2 as indicated.

Shade Exam- on Amine 1 Amine 2 ple cotton

3 Red

4 Red

5 Red

6 Red

7 Red

8 Red

9 Red

10 Red

11 Bluish red

12 Bluish red

13 Bluish red

14 Bluish red

15 Bluish red

16 Bluish red

17 Bluish red

18 Bluish red

19 Bluish red

20 Bluish red

21 Bluish red

22 Bluish red

23 Bluish red

24 Red

25 Red

26 Red

27 Red

28 Violet

29 Violet

30 Violet

31 Violet

32 Violet

33 Violet

34 Violet

35 Violet

36 Violet

37 Violet

38 Violet

39 Violet

EXAMPLE 40

1. Condensation: 10.13 parts of dichloro-sulfophenyl-xanthen were mixedtogether with 4.22 parts of 2-(2-chloro-ethanesulfonyl)-ethylamine asamine 1 in 100 ml of water and the pH was adjusted to 5.0. The reactionmixture was heated to 60° C. and stirred and the pH was kept at 5.0 witha 15% ic Na₂CO₃ solution.

2. Condensation: After 1 hour 4.9 parts2-(2-methylamino-ethanesulfonyl)-ethanol as amine 2 were added and thepH was adjusted to 9.0 and the reaction mixture was heated to 90° C. andstirred for 3 hours.

The reaction mix was cooled to room temperature and the water wasevaporated under reduced pressure delivering 19.3 parts of Intermediate1 after drying under vacuum conditions.

Sulfonation: 17.52 parts of Intermediate 1 were added in portions to 110parts sulfuric acid (98 to 100%) at 20 to 60° C. the reaction mixturewas stirred for 3 h at 60° C. and then cooled to 0 to 5° C. This mixturewas added to 300 parts of ice at 0° C., the pH was adjusted with CaCO₃to 5.3. The CaSO₄ was filtered and the product in the filtrated solutionwas isolated by vacuum rotary evaporation and dried under vacuumconditions resulting in 16 parts of example 1 that dyes cotton inbrilliant fluorescent red shades.

Example 40 EXAMPLE 41 TO 43

According to example 40 and example 2 the following amines can be usedfor 1. Condensation (Amine 1) and for 2. Condensation (Amine 2), aftersulfonation and isolation according to example 1 or 2 dyes having thegiven colours are obtained when using amines 1 and 2 as indicated.

Shade on Amine 1 Amine 2 Expl. cotton

41 Bluish red

42 Bluish red

43 Bluish red

EXAMPLE 44

32.2 parts of phthalic anhydid were added to 246 parts of POCl₃ understirring. After 30 minutes 58 parts of Resorcinol (3-Hydroxy-phenol)were added and the mixture was heated to 95° C. and stirred for 2 hours.The reaction mixture was cooled down to 5° C. and added to 3000 parts ofa 5° C. cold 20% ic aqueous NaCl solution. The suspension was stirredfor 30 minutes at 0 to 5° C. and filtrated. The isolated wet press pastewas suspended in 200 parts of acetone and stirred for 20 minutes at 5°C. After filtration and drying 24.6 parts ofdichloro-carboxyphenyl-xanthen were isolated.

1. Condensation: 9.5 parts of dichloro-carboxyphenyl-xanthen were mixedtogether with 5.73 parts of n-ethyl-3 (β-hydroyethy)sulfonylanilin/(2-(3-ethylamino-benzenesulfonyl)ethanol) in 100 ml of water andthe pH was adjusted to 5.0. The reaction mixture was heated to 60° C.and stirred and the pH was kept at 5.0 with a 15% ic Na₂CO₃ solution.

2. Condensation: After 1 hour 4.9 parts of2-(2-methylamino-ethanesulfonyl)-ethan were added and the pH wasadjusted to 9.0 and the reaction mixture was heated to 90° C. andstirred for 3 hours.

The reaction mix was cooled to room temperature and the water wasevaporated under reduced pressure delivering 19.8 parts of Intermediate1 after drying under vacuum conditions.

Sulfonation: 16.1 parts of Intermediate 1 were added in portions to 90parts sulfuric acid (98 to 100%) at 20 to 60° C. The reaction mixturewas stirred for 3 h at 60° C. and then cooled to 0 to 5° C. This mixturewas added to 250 parts of ice at 0° C., the pH was adjusted with CaCO₃to 5.3. The CaSO₄ was filtered and the product in the filtrated solutionwas isolated by vacuum rotary evaporation and dried under vacuumconditions resulting in 14.9 parts of example 1 that dyes cotton inbrilliant fluorescent red shades.

Example 44 EXAMPLES 45 TO 68

According to example 44 the following amines can be used for the firstcondensation (Amine 1) and for the second condensation (Amine 2). Aftersulfonation and isolation according to example 44 dyes having the givencolours are obtained when using amines 1 and 2 as indicated.

Shade on Amine 1 Amine 2 Expl. cotton

45 Red

46 Red

47 Red

48 Red

49 Red

50 Red

51 Bluish red

52 Bluish red

53 Bluish red

54 Bluish red

55 Bluish red

56 Bluish red

57 Bluish red

58 Bluish red

59 Red

60 Red

61 Red

62 Red

63 Violet

64 Violet

65 Violet

66 Bluish red

67 Bluish red

68 Bluish red

DYEING EXAMPLE 1

3 parts of the dye from example 1 of this invention and 60 parts ofsodium chloride were dissolved in 1000 parts of water and 12 parts ofsodium carbonate and 0.5 parts of a wetting agent were added. Thisdyebath was entered with 100 parts of bleached cotton knitted fabric.The temperature of the dye bath was raised to 30° C. at a gradient of0.5° C./minute and held at this temperature for 30 minutes and thenincreased over 30 minutes to 60° C., this temperature being maintainedfor a further 60 minutes. Thereafter the dyed goods were initiallyrinsed with tapwater for 5 minutes. The dyed goods were neutralized at50° C. using 60% strength acetic acid for 30 to 40 minutes. The goodswere rinsed with boiling tapwater for 30 to 40 minutes followed by afinal rinse at 40 to 50° C. for 20 minutes and dried.

The very brilliant fluorescent bluish red dyeing obtained has goodoverall fastness properties.

1. A dye of formula (I)

wherein in each case independent from each other W is O, S or NH, R¹ andR² is hydrogen, alkyl, alkyl substituted by one or more substituentsselected from the group consisting of methoxy, hydroxy, sulfato, sulfoand chloro, aryl, aryl substituted by one or more substituents selectedfrom the group consisting of chloro, acetylamino, sulfo, hydroxy,carboxy, (C₁-C₄)-alkanoyl, (C₁-C₄)-alkoxy and (C₁-C₄)-alkyl or benzyl,R³ and R⁴ is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy,thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO₃M, COOM,nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl,heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl,acyloxy, aryloyloxy or SO₂—X, wherein X is vinyl or CH₂CH₂—Y, wherein Yis a group removable under alkaline conditions, Z⁻ is selected from thegroup consisting of halogen, sulfate, alkylsulfonate, benzolsulfonate,toluolsulfonate, tetraborofluorate and acetate, A¹ and A² is a spacer offormula (2c) or (2d)

whereby the respective spacer A¹/A² is attached to the chromophore atthe * position and to the respective reactive anchor T¹/T² at the **position, and wherein d is an integer from 1 to 4, e is an integer from0 to 3, f is an integer from 0 to 3, g is an integer from 0 to 3, Q isO, NH or S, R⁶ is hydrogen, halogen, alkyl, N-acylamino, alkoxy,thioalkoxy, hydroxy, alkoxycarbonyl, acyl, arylol, acyloxy, aryloyloxy,cycloalkyl, aryl, SO₃M or COOM, R⁸ and R⁹ is hydrogen, alkyl, alkoxy,aryl, hydroxyl, NH—CH₂—CH₂—OSO₃H, SO₃M or COOM, T¹ and T² is a reactiveanchor of formula (3d), (3e) or SO₂—X

whereby the respective reactive anchor T¹/T² is attached to therespective spacer A¹/A² at the *** position, and wherein X is vinyl orCH₂CH₂—Y, wherein Y is a group removable under alkaline conditions, andM is hydrogen, lithium, sodium, potassium, ammonium, mono-, di-, tri- ortetra-(C₁-C₄)-alkylammonium, one equivalent of an alkali earth metal ora monovalent organic cation.
 2. The dye according to claim 1, wherein ineach case independent from each other W is O or S, R¹ and R² ishydrogen, alkyl, alkyl substituted by one or more substituents selectedfrom the group consisting of methoxy, hydroxy, sulfato, sulfo andchloro, aryl, aryl substituted by one or more substituents selected fromthe group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy,(C₁-C₂)-alkanoyl, (C₁-C₂)-alkoxy and (C₁-C₂)-alkyl or benzyl, R³ and R⁴is hydrogen, (C₁-C₄)-alkyl, hydroxy, aryl, (C₁-C₄)-alkoxy, N-acylamino,halogen, SO₃M, COOM, acyl, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonylor SO₂—X, wherein X is vinyl or CH₂CH₂—Y, wherein Y is a group removableunder alkaline conditions, Z⁻ is selected from the group consisting ofhalogen, sulfate, alkylsulfonate, benzolsulfonate, toluolsulfonate,tetraborofluorate and acetate, A¹ and A² is a spacer of formula (2c) or(2d)

whereby the respective spacer A¹/A² is attached to the chromophore atthe * position and to the respective reactive anchor T¹/T² at the **position, and wherein d is 1 or 2, e is 0 or 1, f is 0, g is 0 or 1, Qis O or S, R⁶ is hydrogen, (C₁-C₄)-alkyl, N-acylamino, (C₁-C₄)-alkoxy,acyl, benzyl, SO₃M or COOM, R⁸ and R⁹ is hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, SO₃M or COOM, T¹ and T² is SO₂—X, wherein X is vinyl orCH₂CH₂—Y, wherein Y is a group removable under alkaline conditions and Mis hydrogen, lithium, sodium, potassium, one equivalent of an alkaliearth metal or a monovalent organic cation.
 3. The dye according toclaim 1, wherein in each case independent from each other W is oxygen,R¹ and R² is hydrogen, (C₁-C₄)-alkyl, aryl, or benzyl, R³ and R⁴ ishydrogen, (C₁-C₂)-alkyl, halogen, SO₃M, COOM or SO₂—X, wherein X isvinyl or CH₂CH₂—Y, wherein Y is a group removable under alkalineconditions, Z⁻ is selected from the group consisting of halogen,sulfate, alkylsulfonate, benzolsulfonate, toluolsulfonate,tetraborofluorate and acetate, A¹ and A² is a spacer of formula (2c-1)or (2d-1)

whereby the respective spacer A¹/A² is attached to the chromophore atthe * position and to the respective reactive anchor T¹/T² at the **position, and wherein d is 1 or 2, e is 0 or 1, g is 0 or 1, Q isoxygen, R⁶ is hydrogen or (C₁-C₂)-alkyl, R⁸ and R⁹ is hydrogen,(C₁-C₂)-alkyl, (C₁-C₂)-alkoxy or SO₃M, T¹ and T² is SO₂—X, wherein X isvinyl or CH₂CH₂—Y, wherein Y is a group removable under alkalineconditions and M is hydrogen, lithium, sodium, potassium, one equivalentof an alkali earth metal or a monovalent organic cation.
 4. A processfor the production of dyes according to claim 1 comprising the steps of:a) Reacting one 3,6,9 substituted 9H-Xanthene, wherein the 3- and6-substituents react as a leaving group, with two precursor-aminesH—NR¹-A¹-T¹ and H—NR²-A²-T² of identical or differentspacer-reactive-anchor-units on 3- and 6-position, and b) Sulfonatingthe OH-groups with concentrated sulfuric acid.
 5. The process for theproduction of dyes according to claim 1 comprising the steps of:reacting one 3,6,9 substituted 9H-Xanthene, wherein the 3- and6-substituents react as a leaving group, with a) two identicalaliphatic-, aromatic- or mixed aliphatic/aromatic-amines symmetricallyon both 3- and 6-position, or b) one aliphatic-, aromatic- or mixedaliphatic/aromatic-amine for the 3-position in a first step and onealiphatic-, aromatic- or mixed aliphatic/aromatic-amine, which isdifferent to the first one, for the 6-position in a second step or c)one aliphatic-, aromatic- or mixed aliphatic/aromatic-amine for the6-position in a first step and one aliphatic-, aromatic- or mixedaliphatic/aromatic-amine, which is different to the first one, for the3-position in a second step and further reacting the products resultingfrom a), b) and c) respectively with reactive anchor groups.
 6. Achemical composition comprising one or more dye(s) according to claim 1.7. An aqueous solution for dying comprising one or more chemicalcompounds according to claim
 1. 8. A process for dyeing or printingcarboxamido- and/or hydroxyl-containing material, comprising contactingthe carboxamido- and/or hydroxyl-containing material with the dyeaccording to claim
 1. 9. An ink digital textile printing, comprising thedye according to claim
 1. 10. A process for dying fibers whichcomprising contact the fibre or blends of the fibres with the dyeaccording to claim 1 wherein the fibres are selected from the groupconsisting of: synthetic fiber materials, nylon materials, nylon-6,nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton,organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp,jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalkfibres, bamboo; fibres from animals, wool, organic wool, silk, cashmerewool, alpaca fiber, mohair, Angora fibre as well as fur and leathermaterials; manufactured, regenerated and recycled fibres, cellulosicfibres; paper fibres, cellulosic regenerated fibres, viscose rayonfibres, acetate and triacetate fibers and Lyocell fibers.
 11. Fiber andblends containing such fiber selected from the group consisting of:synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 andaramid fibres, vegetable fibres, seed fibres, cotton, organic cotton,kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf,ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres,bamboo; fibres from animals, wool, organic wool, silk, cashmere wool,alpaca fiber, mohair, Angora fibre as well as fur and leather materials;manufactured, regenerated and recycled fibres, cellulosic fibres; paperfibres, cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibers, and Lyocell fibers comprising one or more dye(s)according to claim 1, either in chemically and/or physically bound form.12. A process for dying fibers which comprising contact the fibre orblends of the fibres with the chemical composition according to claim 6wherein the fibres are selected from the group consisting of: syntheticfiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres,vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir fromcoconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaffibres, sisal, henequen, banana; stalk fibres, bamboo; fibres fromanimals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair,Angora fibre as well as fur and leather materials; manufactured,regenerated and recycled fibres, cellulosic fibres; paper fibres,cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibers and Lyocell fibers.
 13. A process for dying fiberswhich comprising contact the fibre or blends of the fibres with theaqueous solution according to claim 7 wherein the fibres are selectedfrom the group consisting of: synthetic fiber materials, nylonmaterials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seedfibres, cotton, organic cotton, kapok, coir from coconut husk; bastfibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal,henequen, banana; stalk fibres, bamboo; fibres from animals, wool,organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre aswell as fur and leather materials; manufactured, regenerated andrecycled fibres, cellulosic fibres; paper fibres, cellulosic regeneratedfibres, viscose rayon fibres, acetate and triacetate fibers and Lyocellfibers.